Process for the formation of a sulfurized halogenated aliphatic hydrocarbon



p 1952 N. M. SCHNEIDER ETAL 2,611,766

PROCESS FOR THE FORMATION OF A SULFURIZED HALOGENATED ALIPHATICHYDROCARBON Filed Dec. 28, 1949 ,QEAcT/o/v VESSEL 8 T SEPARATION VESSEL8 M/X/NG VESSEL SEPARATION VESSEL. gg zf FILTER- Patented Sept. 23,19522:11:

rnocEss FOR THE FORMATION or A son- .-FURIZED. HALO'GENATED ALIPHATICH-,

DROCARBON NicholasM. Schneider, Bayonne, andR-aymond M. Dean,Westfield,. N. J.,, assignors toStand 1 ard-Oil Development Company,-.acorporation of Delaware Applicationllecember 28, 1-949, Serial N0.:I35:1 16

' 4 Claims. (01. 260-439") "T i DV I HO 1 M .0 lubricatin O l d-'7ditives. Particularlygit relates to an improved process for themanufacture of lubricating oil additives which have the characteristicof .imparting desirable qualities to lubricating oils with which theyare blended. More particularly, the invention relates to animprovedprocess forthe preparation of ,sulfurized halogenated aliphaticmaterials.

In U. S. Patent 2,124,598 issued July 26, 1938, there is disclosed alubricating oil additive which is made by incorporating sulfur intohalogenated aliphatic compounds. The additive materials disclosed inthis patent have the desirable characteristics of imparting .to alubricating oil blend containing them resistance to extreme pressuresunder high rates of shear.

These lubricating oil additive materials have been made heretofore bycombining with the desired halogenated aliphatic material, such as highmolecular weight hydrocarbons, sulfur in the form of sodiumhydrosulflde, elemental .sulfurand the like. lngeneralrthe process hasinvolved dissolving the halogenated material in a solvent such as analcohol and admixing the sulfur-containing material therewith. After thede-' sired period of time has elapsed and the sulfurization hasreachedthe desired stage, the mixture is allowed to separate into its componentlayers by gravity separation. The top layer, being composed of the majorproportion of the solvent,is withdrawn and recycled for reuse in theprocess. The bottom, or brine, layenfis withdrawn and may be discarded,or approximately of the alcoholis recovered by distillation.

The middle or productlayerwhich contains the sulfurized halogenatedhydrocarbon material also contains entrained-or dissolved therein aminor proportion of the solvent along with extraneous matter such asreaction sludge, sediment and so forth. This entrained or dissolvedsolvent has normally been removed by a process of vacuum stripping.Temperatures in the neighborhood of 200 F. to 255 .F. are used ata-va'cuum of about 18 to-26 inches of mercury." .3

After the stripping step is cormial'eted andthe entrained solvent hasbeen removed the product is then passed through a filtering medium forre- 7 for an extended period of time deteriorates slightly in itsability to impart the above Vmentioned desirable characteristics to thelubricating oil.

Also the vacuum stripping has been done in the reactor vessel itself,thus tying up the-vessel for an undesirably long period soiJiume.

In the improved process which is the subiect of this invention the abovementioned disadvantages are eliminated. The vacuum distilla f tionstepis completely done awavw'ith and sub-j stituted thereforis a processfor the separation of the entrained or entrapped solvent by a si-m-' pleselective solvationprocess. In'thisnew p1 ce'dure the productlayerreferred to above',f that is, that layer containing thesulfurizedihalogen ated hydrocarbon along with a minor amount ofentrained solvent isa'dmixed with a'liquidin which the solvent used issolublelbut in which the product is not soluble. It is to be understood,of course, that the particular liquid chosen will depend upon theparticular. solvent'used in the reaction stage ofthe process; Whenthfesolventusedis an alcohol such as isopropyl alcohol the solubilizingliquid may be .water. i

The mixture of the product layer iandjtheladded liquid is agitated, fora period of time .suflicient to completely dissolve the solvent in.theliquid and the mixture is then allowed: to separateusing a simplegravity separation. The top-layer, which ordinarily will contain thedissolved sol; vent, is withdrawn and .the bottom layer which containsthe product, .freeirom all but traces of entrained solvent, .is airblowntoremove traces of ,solubilizing liquid and solvent and is then passedthrough afilter medium for-theremoval of extraneous material s. v Ifdesired, va,filtering agent such as diatomaceous earthmay-be. addedprior to the-filtering step. :2 ,1

In the drawing there is illustratedan apparatus suit-ablefor carryingout one embodimentrof the invention. .It is to be realized, of course,hat the-apparatus as. shown is not limiting, in any respect since other-:means .ofcarrying outnthe process of this. invention will beevidentsto.those skilled in the art. In this particulanembodiment a-mixture ofchlorinated; wax andchlorine ated kerosene is sulfurized usingelementalsulfur and sodium hydrosulfide. .Isopropyl-alcohol is used as asolvent for thewax-kerosenesmixture. The amounts of these constituentsusedwilldepend uponthe product desired. I

Referring now to the drawing, numeral 2'represents ,a reaction vesselsuitable for carryingout the-sulfurization of the halogenated thydrocarebon material. Through an openingsuch aspcrt 4 the, halogenatedvchlorowax chloro; kerosene mixture is added. .Howevenany of the variouschlorinated hydrocarbons such as chlorinated Wax, chlorinatedpetrolatum, chlorinated .kero: sene, or mixtures of the above in .anydesired proportion maybe added to the reaction vessel at this point.Also through port 4 the sulfurizing agent,,-elemental, sulfur and sodiumhydrosulfide is added. -Sodium isulfide,q.or,,;any :rofythepolysulfidesmay be; added. to .athexreaction. yes: i

r se1;at-this-pointwhen:itsisdesiredz togusethese;in-

Any of the lower alcohols, v,

isopropyl alcohol usually being preferred, may

be used. 7 l

The mixture in the reaction vessel is agitated for the desired period oftime, usually 2 to 6 hours at reflux temperature, by meansoi anagitation device such as propeller 8 which is driven by shaft l and anelectric motor I2. Suitable heating means such as a steam coil, notshown, may be used to raise the temperature of the ingredients in thereaction vessel to the desired level. Preferred temperatures will bewithin a range of from 160 F. to 180 F. When the reaction between thesulfur compound and the halogenated hydrocarbon has proceeded to thedesired point, the agitation is suspended and the contents of thereaction vessel are withdrawn through valved line l4' into a separationvessel 16. Here the mixture is allowed to separate by gravityseparation. This usually requires from 15 minutes to 2 hours dependingupon the constituents of the mixture; In the preferred embodiment, thisseparation will occur within from 15 minutes to 1 hour.

Three layers are formed on standing in separation vessel l6. The bottomlayer which contains any of the excess sodium salt and any unused sulfuris withdrawn from vessel [6 through valved lines I8 and 20. Ordinarilythis material is discarded. The middle or product layer which containsthe sulfurized halogenated hydrocarbon material and a certain amount ofthe alcohol entrapped or dissolved is withdrawn through valved line l8and introduced through valved line 22 into mixing vessel 24. The toplayer, which contains the major proportion of the alcohol used iswithdrawn through valved as propeller driven by shaft 32 and electric 7'motor 34, the desired amount of agitation is obtained. The temperaturedesired in mixing vessel may be obtained by means of a suitable heatingdevice, such as a steam coil, not shown. Preferred temperatures arethose between 70 F. and 150 F.

The mixture of water and product is agitated to insure completesolubilization of the alcohol which ordinarily will take from 15 minutesto 3 hours, depending upon type of agitation.

After the mixing is completed the contents of mixing vessel 24 arewithdrawn through valved line 3-6 into separation vessel 38. Heregravity separation is allowed to occur again. The product layer freedfrom substantially all of the entrained solvent is removed throughvalved lines 40 and 42 and introduced into aeration vessel 46. The waterlayer containing dissolved therein substantially all of the alcoholwhich was entrapped by the product layer is removed through valved lines40 and 48. I In aeration vessel 46 the product, which may contain aminor amount of entrapped water alcohol mixture is blown with air whichis 'in-, troduced into the bottom of the aeration "vessel aenyec Tb...5; f xiii '4 through valved lines 58. The blowing with the air removesany of the entrapped liquid leaving the product free and clear exceptfor minor amounts of extraneous materials such as reaction sludge,sediments, and the like.

The product is then withdrawn from aeration vessel 46 through valvedline 52 and introduced into a filtering device as shown at 54. Thisfiltering device may be any of the various filters known to the art suchas a plate and frame press, and the like. If it is desired a filter aidsuch as diatomaceous earth may be added to the product in the aerationvessel to aid in the filtering operation. 7 I This invention will bemore completely described and moreclearly explained by'a reference tothe following examples. I

A mixture of 60 parts of chlorinated kerosene (41.0% chlorine) and 40parts of chlorinated wax (34% chlorine based on pts.) was-reacted with3.2 parts of elemental sulfur and58.5 parts of 25% aqueous sodiumhydrosulfidein the presence of parts of isopropyl alcohol as a solvent.After 3 hours at 176 F. the re-' action mixture was allowed to separateinto three layers.

Four 500 milliliter portions of the middle or product layer were taken.One portion wassubjected to a vacuum distillation step. The (3113tillation was carried out at a temperature between 215 F. and 220 F. forone half hour at 26 inches of mercury. An inspection of the productafter the distillation was completed showed that it was free of alcohol.This sample was labeled Example IV.

The remaining three portions of the product', Examples I, II and III,were each agitated with milliliters of water until the alcohol wascompletely dissolved. The mixtures were then allowed to separate and theproduct layers withdrawn from the water layers. The separated productlayers were then blown with air to remove any residual water-alcoholsolution.

The temperatures of the water washing and air blowing steps with thesettling time and-the blowing time are given in Table I belowzl TABLE IWater Washing Air Blowing Example Temp. as Temp. .Time

F. I hrs. F. hrs.

70 3 7O 2% II 100 3 100 2% m 125 s 125 2 The four examples treated asdetailed' above were then tested for. per cent chlorine; per cent sulfurand viscosity at 210 F. Results are shown in Table II below?" TABLE IIInspection test data Percent Percent Percent Viscosity Example ChlorineSulfur Gravity (S' 30.5 5.9 17.9 61.0 30.6 5.9 17.9 .61.2 30.6 an 18.061.2 33.5 5.8 17.8 -e1.:'

1 This sample of product was vacuum distilled at a temperature of 2l5220F. for 0118 11811 under-g6 inches of mercury to remove excess isopropylalcohol. J p 4.15;. j (I The data in Table II above shows that there isno differentiation in the final products of the two processes as regardsto the per cent chlorine, per cent sulfur, and viscosity at 210 F., alltests agreeing within experimental error.

The materials of Examples I through IV were then tested as to theirsolubility in different base Oil A=a paraflinic aviation oil having aviscosity at 210 F of 76-84 S. U. S. and a viscosity index of 100.

1 Oil B=50% of a propane deasphalted phenol treated residuum fromPanhandle Crude having a viscosity of 210 F. of 160-170 S. U. S. and aviscosity index of 90 with 50% of a treated and filtered paraflinicdistillate having a viscosity at 100 F. of 285-295 S. U. S. and aviscosity index of 72.

1 This sample of product was vacuum distilled at a temperature of215220.F. for one-half hour under 20 inches of mercury to remove excessisopropyl alcohol.

That the additive material manufactured according to the process of thisinvention is equally potent with that material made by the old processis conclusively pointed out by the data given in Table IV.

by weight of the product was blended with test Oil C and was subjectedto the tests as reported below:

1 Oil C=69% of a steam refined cylinder stock from a Pennsylvania Crudehaving a viscosity at 210 F. of 210-225 S. U. S. with 31% of a treatedparaflin distillate having a viscosity at 210 F. of 285-295 S. U. S. anda viscosity index of 72. I

I This sample of product was vacuum distilled at a temperature of 2l5220F. for one-ha1i hour under 26 inches of mercury to remove excessisopropyl alcohol.

To summarize briefly, this invention involves an improved process forthe formation of sulfurized halogenated hydrocarbon materials. In theprocess an expensive time-consuming vacuum stripping step is eliminatedand substituted therefor is a simple procedure for accomplishing thesame end, that is, removing any entrained solvent by dissolving theentrained solvent with a liquid in which it is soluble, separating theliquid-solvent mixture, and removing any minor amount of the liquid fromthe product by blowing with air.

What is claimed is:

1. A process for the formation of a sulfurlzed halogenated aliphatichydrocarbon which comprises subjecting a mixture of chlorinated wax andchlorinated kerosene to the action of elemental sulfur and sodiumhydrosulfide in the presence of an alcohol as a solvent in a reactionzone, allowing the reaction to proceed for the desired period of time,permitting the reaction mixture to separate into three layers,discarding the bottom brine layer, recycling the top alcohol layer tothe reaction, removing the middle product layer to a mixing zone andadding thereto water, mixing said product and said added water for untilthe alcohol entrained with said product is dissolved, allowing saidmixture to separate into two layers, a top layer and a bottom productlayer, removing the top layer from said mixing zone, removing the bottomproduct layer to a second mixing zone, blowing the removed product layerwith a gas to remove any residual solubilizing agent and solvent,removing the blown product to a filtering zone, and filtering saidproduct to remove extraneous material.

2. A process according to claim '1 wherein the solvent used is isopropylalcohol.

3. A process according to claim 1 where the gas used is air.

4. A process for the formation of a sulfurized halogenated aliphatichydrocarbon having the. characteristic of imparting desirable extremepressure resisting properties to a lubricating oil with which it isblended which comprises subjecting a mixture of chlorinated wax andchlorinated kerosene to the action of elemental sulfur and sodiumhydrosulfide for from 2 to 6 hours in a reaction zone heated to atemperature of from F. to F. in the presence of isopropyl alcohol as asolvent, withdrawing the product into a settling zone, allowing theproduct to separate into three layers, discarding the bottom brinelayer, recycling the top alcohol layer to the reaction zone, removingthe middle product layer to a mixing zone and adding thereto 5 to 25parts of Water, raising the temperature of said mixing zone to onewithin the range of from 70 F. to 150 F., agitating the product in saidmixing zone for from A to 3 hours, withdrawing the mixture into a secondseparation zone, allowing the mixture to separate into two layers, a topwateralcohol layer and a bottom product layer, withdrawing said topwater-alcohol layer from said separation zone, introducing said bottomproduct layer into a separate mixing zone, blowing said product in saidsecond mixing zone with air heated to a temperature Within a range offrom room temperature to 200 F. for from 1 to -5 hours in said secondmixing zone to remove any residualwater, removing the blown product to afiltering zone, and filtering said blown product to remove extraneousmaterial.

NICHOLAS M. SCHNEIDER. RAYMOND M. DEAN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,124,598 Turner July 26, 19382,192,700 Turner Jul 26, 1938

1. A PROCESS FOR THE FORMATION OF A SULFURIZED HALOGENATED ALIPHATICHYDROCARBON WHICH COMPRISES SUBJECTING A MIXTURE OF CHLORINATED WAX ANDCHLORINATED KEROSENE TO THE ACTION OF ELEMENTAL SULFUR AND SODIUMHYDROSULFIDE IN THE PRESENCE OF AN ALCOHOL AS A SOLVENT IN A REACTIONZONE, ALLOWING THE REACTION TO PROCEED FOR THE DESIRED PERIOD OF TIME,PERMITTING THE REACTION MIXTURE TO SEPARATE INTO THREE LAYERS,DISCARDING THE BOTTOM BRINE LAYER, RECYCLING THE TOP ALCOHOL LAYER TOTHE REACTION, REMOVING THE MIDDLE PRODDUCT LAYER TO A MIXING ZONE ANDADDING THERETO WATER, MIXING SAID PRODUCT AND SAID ADDED WATER FOR UNTILTHE ALCOHOL ENTRAINED WITH SAID PRODUCT IS DISSOLVED, ALLOWING SAIDMIXTURE TO SEPARATE INTO TWO LAYERS, A TOP LAYER AND A BOTTOM PRODUCTLAYER, REMOVING THE TOP LAYER FROM SAID MIXING ZONE, REMOVING THE BOTTOMPRODUCT LAYER TO A SECOND MIXING ZONE, BLOWING THE REMOVED PRODUCT LAYERWITH A GAS TO REMOVE ANY RESIDUAL SOLUBILIZING AGENT AND SOLVENT,REMOVING THE BLOWN PRODUCT TO A FILTERING ZONE, AND FILTERING SAIDPRODUCT TO REMOVE EXTRANEOUS MATERIAL.